I'm going to be taking some shots of my family this weekend. I've checked and sunset is 5:38. So question 1 is in November, how close to 5:30 will I most likely to be able to shoot? I'm thinking I should start at 3:30 to be sure that the photos in the covered bridge have enough light.

I've scouted the location we're going to take pictures and taken some quick snapshots to test the backgrounds. I've made a basic list of shots I want to take in different locations to make sure I don't forget to take a picture of my daughter by the creek for example. I'm planning to have 2 camera bases set up - My 5d and my rebel t4i. I'm planning to use my 85 mm lens and the 70-200mm lens.
I have a fill flash, a tripod and I've practiced with my remote so I can be in a couple of shots as well. What else should I think about before hand?

Obviously these are my family photos, so noone is paying me for these. I'm both excited and nervous about it. But I know that I calm down when I've planned things out.

Any additional tips for me. We'll be working fast with a 2 year old and 3 year old.

I've got us in coordinating but not matching outfits. So my husband will be in a brown sweater, I'm in a red top with a cream sweater over it. My son is wearing red and khakis, and my daughter is in a cream dress with red accents. So everyone is in the same color palette but not the same outfits.

Scout the location at the time of day; there are very often shadows and other issues that are not readily apparent at different times. I definitely wouldn't start any later than 3.30 if sunset is 5.38, but depending on geography (ie, your shoot location is a deep valley) it might need to be even earlier. It sounds like you've got things pretty well sussed. Good luck!

Golden hour is the hour right before sunset so starting at 4:38. Your 2 and 3 year old are going to be done with the photos after 20 minutes max. If you start at 3:30 you won't have the golden hour glow and I doubt your kids will make it to 4:30. That's just my experience with little ones. After the 20 minute mark with kids they start acting up...parents start yelling thinking their kids will magically cooperate and things get unpleasant pretty quick.

I always say keep clothing neutral with a pop of colour. I'm not sure where you are from but here can be crazy cold so I say no puffy jackets just sweaters. If it's really cold it's cute to have hat's and mitts on the little ones....or jacket vests...if that makes sense.

Sorry, I just noticed you talked about wardrobe above...your choices sound really nice

Below is a photo of my daughter I took literally 5 minutes before the sunset. It was really cutting it close and not as bright as I would have liked...but still worked.

"Golden hour" isn't a finite amount of time, rather it's a period shortly before sunset/after sunrise when the light is most pleasant, and it's time and duration depend on many factors including season/time of year, weather, and local geography. If you start a family shoot at 3.30, you probably won't actually start shooting until about 3.50 - 4.00pm, and once you get to that last hour before sunset, depending on local geography, you can be faced with some serious shadows. Bring some toys for the kids and let them muck about in between sets.